CN104437558B

CN104437558B - A kind of novel green solid super acid catalyst for cyclohexanone self-condensation reaction and its application

Info

Publication number: CN104437558B
Application number: CN201410661345.1A
Authority: CN
Inventors: 孙国新; 程沙沙; 崔玉
Original assignee: University of Jinan
Current assignee: University of Jinan
Priority date: 2014-11-19
Filing date: 2014-11-19
Publication date: 2017-03-01
Anticipated expiration: 2034-11-19
Also published as: CN104437558A

Abstract

The invention discloses a kind of preparation method and applications of the novel green solid super acid catalyst for cyclohexanone self-condensation reaction, this catalyst is to self condense two kinds of resonance isomer A of generation in Ketohexamethylene₂And A₃Reaction in use（A₂、A₃It is 2 respectively（1 cyclohexenyl group）Ketohexamethylene and 2 hexamethylene alkylene pentylcyclohexanone）, belong to catalysis technical field.The present invention prepares this catalyst using infusion process, first by required La（NO₃）₃·6H₂O、Ce（NO₃）₃·6H₂O、（NH₄）₂SO₄It is dissolved in distilled water, next puts into required nanometer ZrO₂, impregnated, be dried to anhydrous, calcine to obtain SO₄ ^2‑·xLa³⁺·yCe³⁺/zZrO₂.This catalyst is applied in cyclohexanone self-condensation reaction, in 130 170 DEG C of reaction temperature, catalyst SO₄ ^2‑·xLa³⁺·yCe³⁺/zZrO₂Consumption 1 10, response time 1 3h, up to more than 80, dimer selectivity can reach more than 95% to Ketohexamethylene conversion ratio.

Description

A kind of novel green solid super acid catalyst for cyclohexanone self-condensation reaction and Its application

Technical field

Invention describes a kind of preparation of the novel green solid super acid catalyst for cyclohexanone self-condensation reaction Method and its application, this catalyst is to use in Ketohexamethylene condensation reaction, belongs to catalysis technical field.

Technical background

2-（1- cyclohexenyl group）Ketohexamethylene and its resonance isomer be two step synthetic method o-phenyl phenol important intermediate. O-phenyl phenol is industrially product in the middle of important fine chemistry industry, has a wide range of applications in chemical field, with economical Fast development, the consumption of o-phenyl phenol is also increasing.In view of depositing in the important use of o-phenyl phenol, and current production Problem, develop, the o-phenyl phenol production technology of the new environmental safety type of exploitation has just become the task of top priority, continue deeper into out Open up working and striving for that industrialization is also highly desirable to early of this respect.

The method of production o-phenyl phenol has following several：

1st, reclaim OPP, because this partition method yields poorly it is impossible to meet gradually in the bottoms being produced phenol by sulfonation method The market demand increasing, therefore this technique is eliminated already；

2nd, dibenzofuran method：Dibenzofurans are heated at 200 DEG C with metallic sodium, then uses sour decomposition product, obtain O-phenyl phenol.The OPP purity of this technique productions is high, but cost intensive, it is not suitable for industrialized production；

3rd, aminobphenyl diazonium Hydrolyze method：

This route first obtains adjacent phenylaniline with biphenyl nitrification, reduction, then through diazotising, hydrolysis, the step such as refine Come OPP processed.To analyze from the angle of experiment, this route is feasible, but, yet suffer from a lot of weak points at present. Such as raw materials for production 2- aminobphenyl complex process, relatively costly, and toxicity is very big, three-protection design is costly.Generally speaking, This technique is very immature, and industrial value is little；

4th, biphenyl sulfonation Hydrolyze method：

By biphenyl oleum sulfonation, then carry out alkali fusion with sodium hydroxide, then products therefrom acidifying is produced Although this technique technical process of thing OPP is simple, cost of equipment is low, three wastes outstanding problem, belongs to the process route being eliminated；

5th, chlorobenzene-phenol coupled method：With chlorobenzene and phenol as raw material, using phase transfer catalysis process synthesizing o-phenylphenol. This process route had been once the main mode of production of OPP, but due to seriously polluted, this process route is gradually washed in a pan in recent years Eliminate；

6th, biphenyl halo Hydrolyze method：

This process route is first biphenyl chlorination to be generated adjacent phenyl chlorobenzene, and then hydrolysis obtains OPP.This process and chlorine It is similar that phenol is prepared in benzene hydrolysis, needs highly basic and high-temperature and high-pressure conditions, production cost is higher；

7th, Ketohexamethylene condensation dehydriding：

This route is that recent domestic OPP producer adopts more process route.It is Ketohexamethylene first in acid or alkali Under catalytic action, condensation generates dimer, then generates OPP by separating the dimer dehydrogenation obtaining.Because cyclohexanone starting materials are easy , low cost, entirely simple for process, the environmental safety of particularly technique, it is allowed to better than above several process routes.This The second step dimer dehydrogenation reaction of route, its technique is quite ripe, and first step cyclohexanone self-condensation reaction technique road Line is also to be studied.

Both at home and abroad substantial amounts of research carried out to Ketohexamethylene condensation synthesis technique at present, patent CN1371897A and CN1490293A all refer to use dense H₂SO₄Make catalyst.Use dense H₂SO₄It is traditional production method as catalyst although hexamethylene The conversion ratio of ketone increases, but the high dehydrated energy being had by concentrated sulphuric acid and strong oxidizing property, so that selectivity is declined, secondary anti- Should also make impurity content in crude product higher.Additionally, the sulfuric acid corrosion resistance as catalyst is big, the requirement to equipment is higher, So input ratio is larger in advance；In addition, due to cannot recycling be used by alkali liquor neutralization, this is for enterprise for acidic catalyst There is loss in economic benefit again；Finally, due to containing a large amount of salkali waste and other side-products, there is also larger in the aqueous phase after neutralization Environmental issue.

CN1535945A and United States Patent (USP) US4171326 all have studied ion-exchange resin catalyzed Ketohexamethylene condensation, ion Exchanger resin uses for a long time at high temperature, easy in inactivation, is not suitable for industrialized production Ketohexamethylene dimer.

CN102126940A, CN102557908A, CN101613262A, CN101003471A, CN102500398 all study With solid super-strong acid or the condensation of solidity acid as catalyst catalysis of pimelinketone.Generally existing Ketohexamethylene conversion ratio is low or dimer The property selected difference or severe reaction conditions or have the shortcomings that particular/special requirement to equipment.The conversion of Ketohexamethylene in such as CN102557908A Rate is only 45-65%.

CN101205170A and CN102311326A all have studied soild oxide and make catalyst, and overcoming can not serialization Produce, the shortcomings of catalyst system and catalyzing lock out operation is loaded down with trivial details, but in CN101205170A the response time be 4-8h, the cycle is oversize, and Need to be passed through 250 DEG C of circulating heat conduction oils in CN102311326A after the completion of reaction, power consumption is high, therefore both catalyst economy Benefit is not high.

CN101538196A have studied the organic acid as catalyst of aromatic sulfonic acid class, needs during the course of the reaction to control absolute pressure In 30-100KPa, high energy consumption, and aromatic sulfonic acid is easily dissolved each other with Ketohexamethylene and its dimer for Organic substance, is not readily separated.

The solid super acid catalyst SO that the present invention adds₄ ^2-·xLa³⁺·yCe³⁺/zZrO₂, by introduce rare earth metal and Metal-oxide, both ensure that active component SO₄ ^2-Not easily run off during the course of the reaction, additionally provide suitable specific surface area, increasing Add acid site density, strengthened antitoxin thing ability, improve mechanical strength etc., and be easy to get, free from environmental pollution, easy reclaim and can weigh Multiple use, is a kind of environmentally friendly solid catalyst, suitable industrialized production.

Content of the invention

The present invention is directed to the problems such as current Ketohexamethylene conversion ratio is relatively low, and dimer yield is relatively low, in production, waste liquid is difficult, A kind of SO is proposed₄ ^2-·xLa³⁺·yCe³⁺/zZrO₂Catalyst, by adding this solid super acid catalyst in reaction system, The activity of reaction is increased with this, reduces side reaction, to increase the yield of reaction.Urge it is a further object of the present invention to provide above-mentioned Agent self condenses, in Ketohexamethylene, the application generating in dimer.The catalyst making step of the present invention is as follows：First will be required La（NO₃）₃·6H₂O、Ce（NO₃）₃·6H₂O、（NH₄）₂SO₄It is dissolved in distilled water, be then placed in required nanometer ZrO₂, warp Impregnate, be dried, calcine to obtain SO₄ ^2-·xLa³⁺·yCe³⁺/zZrO₂.This catalyst is applied in cyclohexanone self-condensation reaction, reaction Temperature 130-170 DEG C, catalyst SO₄ ^2-·xLa³⁺·yCe³⁺/zZrO₂Consumption be 1-10, response time 1-3h, hexamethylene Up to more than 80, dimer selectivity can reach more than 95% to ketone conversion ratio.

Nanometer ZrO of the present invention₂Particle size is 10-100 mesh, active component SO₄ ^2-Sulfur from variable concentrations Acid solution and（NH₄）₂SO₄, add nanometer ZrO₂Granule can make the solid super-strong acid surface area of generation big, increases catalyst Thermostability.

Active component La of the present invention³⁺And Ce³⁺From the chloride of lanthanum and cerium, sulfate, nitrate and any Soluble-salt, adds La³⁺And Ce³⁺Effectively increase the activity and selectivity of major catalyst as promoter.

The ZrO adding in the present invention₂With（NH₄）₂SO₄Mass ratio be 0.1-2, preferably 1；La（NO₃）₃·6H₂O with （NH₄）₂SO₄Mass ratio be 0.01-0.1, preferably 0.05, Ce（NO₃）₃·6H₂O with（NH₄）₂SO₄Mass ratio be 0.01- 0.1, preferably 0.2.

Dip time of the present invention is 12-48h, and calcining heat is 500-600 DEG C, and calcination time is 2-6h.

Brief description

Accompanying drawing 1 is the reactant liquor gas chromatogram of embodiment 2, and reactant liquor described by accompanying drawing 1 for the accompanying drawing 2 is through vacuum distillation The infrared spectrogram of gained dimer.

Specific embodiment

Reference examples：Add 300ml Ketohexamethylene in 500ml reaction bulb, add concentrated sulphuric acid 15 ml, Ketohexamethylene carries in itself Water preparation, reacts 2h, Ketohexamethylene conversion ratio 55, dimer selectivity 73 at 170 DEG C.

Embodiment 1：First by 1gLa（NO₃）₃·6H₂O、1gCe（NO₃）₃·6H₂O、100g（NH₄）₂SO₄It is dissolved in distilled water In, it is then placed in 10g nanometer ZrO₂, impregnate 36h at 20 DEG C, drying is extremely anhydrous, calcine 5h at 550 DEG C, obtains catalyst SO₄ ^2-·xLa³⁺·yCe³⁺/zZrO₂.Add 1.3L Ketohexamethylene in 2L reaction bulb, add the catalyst being obtained to be Ketohexamethylene matter The 5% of amount, reacts 2.5h at 160 DEG C, reactant liquor is done chromatography of gases and analyzes to obtain Ketohexamethylene conversion ratio 85%, dimer selectivity For 96.5%.

Embodiment 2：First by 2gLa（NO₃）₃·6H₂O、2gCe（NO₃）₃·6H₂O、100g（NH₄）₂SO₄It is dissolved in distilled water In, it is then placed in 25g nanometer ZrO₂, impregnate 36h at 20 DEG C, drying is extremely anhydrous, calcine 5h at 550 DEG C, obtains catalyst SO₄ ^2-·xLa³⁺·yCe³⁺/zZrO₂.Add 1.3L Ketohexamethylene in 2L reaction bulb, add the catalyst being obtained to be Ketohexamethylene matter The 5% of amount, reacts 2.5h at 160 DEG C, reactant liquor is done chromatography of gases and analyzes to obtain Ketohexamethylene conversion ratio 93.2%, dimer selects Property be 97.1%.

Embodiment 3：First by 5gLa（NO₃）₃·6H₂O、5gCe（NO₃）₃·6H₂O、100g（NH₄）₂SO₄It is dissolved in distilled water In, it is then placed in 100g nanometer ZrO₂, impregnate 36h at 20 DEG C, drying is extremely anhydrous, calcine 5h at 550 DEG C, obtains catalyst SO₄ ^2-·xLa³⁺·yCe³⁺/zZrO₂.Add 1.3L Ketohexamethylene in 2L reaction bulb, add the catalyst being obtained to be Ketohexamethylene matter The 5% of amount, reacts 2.5h at 160 DEG C, reactant liquor is done chromatography of gases and analyzes to obtain Ketohexamethylene conversion ratio 98.3%, dimer selects Property be 98.7%.

Embodiment 4：First by 7gLa（NO₃）₃·6H₂O、7gCe（NO₃）₃·6H₂O、100g（NH₄）₂SO₄It is dissolved in distilled water In, it is then placed in 150g nanometer ZrO₂, impregnate 36h at 20 DEG C, drying is extremely anhydrous, calcine 5h at 550 DEG C, obtains catalyst SO₄ ^2-·xLa³⁺·yCe³⁺/zZrO₂.Add 1.3L Ketohexamethylene in 2L reaction bulb, add the catalyst being obtained to be Ketohexamethylene matter The 5% of amount, reacts 2.5h at 160 DEG C, reactant liquor is done chromatography of gases and analyzes to obtain Ketohexamethylene conversion ratio 97%, dimer selectivity For 97.8%.

Embodiment 5：First by 10gLa（NO₃）₃·6H₂O、10gCe（NO₃）₃·6H₂O、100g（NH₄）₂SO₄It is dissolved in distillation In water, it is then placed in 200g nanometer ZrO₂, impregnate 36h at 20 DEG C, drying is extremely anhydrous, calcine 5h at 550 DEG C, obtains catalyst SO₄ ^2-·xLa³⁺·yCe³⁺/zZrO₂.Add 1.3L Ketohexamethylene in 2L reaction bulb, add the catalyst being obtained to be Ketohexamethylene matter The 5% of amount, reacts 2.5h at 160 DEG C, reactant liquor is done chromatography of gases and analyzes to obtain Ketohexamethylene conversion ratio 94%, dimer selectivity For 96.4%.

Claims

1. a kind of preparation method of the solid super acid catalyst for cyclohexanone self-condensation reaction, this catalyst is in Ketohexamethylene Self condense two kinds of resonance isomer A of generation₂And A₃Reaction in use, A₂、A₃It is 2- respectively（1- cyclohexenyl group）Ketohexamethylene and 2- Hexamethylene alkylene pentylcyclohexanone, preparation process is as follows：First by required La（NO₃）₃·6H₂O、Ce（NO₃）₃·6H₂O、（NH₄）₂SO₄It is dissolved in distilled water, be then placed in required nanometer ZrO₂, impregnated, be dried to anhydrous, calcine to obtain SO₄ ^2-·xLa³⁺· yCe³⁺/zZrO₂, calcining heat be 400-600 DEG C；This catalyst is applied in cyclohexanone self-condensation reaction, reaction temperature 130- 170 DEG C, catalyst SO₄ ^2-·xLa³⁺·yCe³⁺/zZrO₂Consumption be Ketohexamethylene quality 2-10, response time 1-3h, Ketohexamethylene conversion ratio reaches more than 80, and dimer selectivity reaches more than 90%；The ZrO adding₂With（NH₄）₂SO₄Mass ratio be 0.2-2, La（NO₃）₃·6H₂O with（NH₄）₂SO₄Mass ratio be 0.01-0.1, Ce（NO₃）₃·6H₂O with（NH₄）₂SO₄Matter Amount ratio is 0.01-0.1.

2. the preparation method of a kind of solid super acid catalyst for cyclohexanone self-condensation reaction as described in claim 1, It is characterized in that：Described ZrO₂With（NH₄）₂SO₄Mass ratio be 1；La（NO₃）₃·6H₂O with（NH₄）₂SO₄Mass ratio be 0.05；Ce（NO₃）₃·6H₂O with（NH₄）₂SO₄Mass ratio be 0.05.

3. the preparation method of a kind of solid super acid catalyst for cyclohexanone self-condensation reaction as described in claim 1, It is characterized in that：Nanometer ZrO₂Particle size is 10-100 mesh.

4. the preparation method of a kind of solid super acid catalyst for cyclohexanone self-condensation reaction as described in claim 3, It is characterized in that：Described nanometer ZrO₂Particle size is 60 mesh.

5. the preparation method of a kind of solid super acid catalyst for cyclohexanone self-condensation reaction as described in claim 1, It is characterized in that：Active component SO₄ ^2-Derive from（NH₄）₂SO₄.

6. the preparation method of a kind of solid super acid catalyst for cyclohexanone self-condensation reaction as described in claim 1, It is characterized in that：Active component La³⁺And Ce³⁺Nitrate from lanthanum and cerium.

7. the preparation method of a kind of solid super acid catalyst for cyclohexanone self-condensation reaction as described in claim 1, It is characterized in that：Dip time is 12-48h, and dipping temperature is 0-40 DEG C.

8. the preparation method of a kind of solid super acid catalyst for cyclohexanone self-condensation reaction as described in claim 7, It is characterized in that：Described dip time is 36h, and dipping temperature is 20 DEG C.

9. the preparation method of a kind of solid super acid catalyst for cyclohexanone self-condensation reaction as described in claim 1, It is characterized in that：Calcination time is 2-6h.

10. the preparation method of a kind of solid super acid catalyst for cyclohexanone self-condensation reaction as described in claim 1, It is characterized in that：Described calcining heat is 550 DEG C, and calcination time is 5h.

The solid super acid catalyst of the 11. preparation method preparations as described in claim 1 is used for cyclohexanone self-condensation reaction, its It is characterised by：Catalyst in cyclohexanone self-condensation reaction, reaction temperature 130-170 DEG C；Catalyst SO₄ ^2-·xLa³⁺·yCe³ ⁺/zZrO₂Consumption be Ketohexamethylene quality 2-10；Response time is 1-3h.

12. cyclohexanone self-condensation reactions as described in claim 11 it is characterised in that：Described reaction temperature is 160 DEG C, catalysis Agent SO4^2-·xLa³⁺·yCe³⁺/zZrO₂Consumption be Ketohexamethylene quality 5；Response time is 2.5h.